Method of producing gasoline



Patented June 13, 1933 UNITED STATES PATENT OFFICE CARY R. WAGNER, OF CHICAGO, ILLINOIS, ASSIGNOR TO THE PURE OIL COMPANY, OF

CHICAGO, ILLINOIS, A CORPORATION OF OHIO I METHOD OF PRODUCING GASOLINE No Drawing. Original application died June 5, 1928, Serial No. 283,145. Divided and this application filed October 10. 1929. Serial No.39 8,812.

This invention relates to the improved process of manufacturing gasoline-like hydrocarbons from unsaturated hydrocarbon gases, and has for its primary object the provision of a novel method of treating unsaturated hydrocarbons such as ethylene, propylene and butylene, especially hydrocarbons of the ethylene series, whereby to effect the polymerization of such light hydrocarbons for the purpose of securing hydrocarbons of higher molecular weights which have the characteristics of gasoline and are suitable for use as motor fuels. The present application is a division of my rior application relating to the same su ject Serial No. 283,145, filed June 5, 1928.

In accordance with the present invention, a body of unsaturated hydrocarbon gases of the character aforesaid and obtained, for example, from pyrogenic treatment of hydrocarbon oils is heated to atemperature inexcess of 350 F. but not in excess of 700 F. When so heated the gases are maintained under super-atmospheric pressures varying between 600 to 1500 pounds per square inch or higher. These temperatures and pressures w1ll, of course, vary in accordance with the characteristics of the hydrocarbon compounds-under treatment, and for this reason 1t is practically impossible to give ,optimum operating conditions of a detailed character. However, for the purpose of the invention it may be stated that the operating temperatures of the gases during the polymerization reactions exceed 350 F. but not in excess of 700? F. and the pressures main promoting the polymerization reactions Among the catalysts suitablefor the purpose of the invention are In'etals belong-- ing to' the 8th group of the periodic series such, for example, as palladium sponge or platinum sponge or alloys thereof possessing very extended surfaces which are capable of adsorbing gases in considerable quantity.

high concentrations locally of these unsaturated gases and thus promote reactions of' the desired polymerization type.

By bringing the hydrocarbon gases of the character set forth under temperature and pressure conditions specified into intimate contact with an adsorbent or catalyst of the type disclosed the unsaturated hydrocarbons such as ethylene, C H propylene C H and butylene H, which have what is known as a double bond, are capable of reacting chemically through polymerization to ,form additive compounds. By adjusting the temperatures and pressures, according to the composition of the mixture of gases, I provide for the controlof the reactions in the formation of additive compounds of higher molecular weight. It is, of course, impossible to set forth the specific temperatures and pressures for all possible combinations of ethylene, propylene, l-butene, 2-butene and isobutene which ma be present, since there. are possible many undreds of different combinations of these hydrocarbons, no two of which would require exactly the same temperature and pressure for most efi'ective operation. The temperatures and pressures above given, however, will enable a skilled worker in the art to readily determine the most efiicient conditions. Through the regulation of these conditions the polymerized compounds can be kept at such molecular weights as to render them suitable particularly for use as motor fuels. 7 I

Any suitable apparatus may, of course, be

used in the heating of the hydrocarbons, in

maintaining super-atmospheric pressures thereon and in the matter of bringing these hydrocarbons under the conditions specified into contact with the catal st. By the present invention a waste product or a product of low economic value ma 4 be transformed into a more useful and va uable product.

Hydrocarbons of the ethylene series are developed in larger quantities in certain types of oil cracking systems, especially those systems pperating at high tempera.- tures and under low pressures. Usually, in such sy'stems'the gases, following condensa- 50 These substances by selective adsorption give tion, are passed to a compressor system f where they are stripped of their more readily condensable products. \Vhile a large percentage of gasoline is recovered by this compressor method of abstraction yet there remains a large'quantity of fixed gas which has little economic value and is generally used for combustion purposes in oil refineries. In some instances it may be used as an enriching gas to raise the B. t. n. values of water gas in localities where industrial conditions permit of economic transfer of gaseous products. However, by the present invention these heretofore practically worthless gases are transformed into a liquid product having the characteristics of high grade gasoline or motor fuels, and the final product obtained by the present invention is intended chiefly for this usage.

The invention has the advantage of being simple and convenient to operate in commercial installations and the recovery of liquid products obtained thereby renders vapor phase systems of oil conversion more economic from a practical standpoint in that the total percentage of recovered inotor fuel of the charging stock employed compares very favorably with the percentage obtained from the well-known liquid phase methods of conversion.

What is claimed is: I

1. The process of manufacturing gasolinelike hydrocarbons from unsaturated hydrocarbon gases of the ethylene series, which consists in heating such gases to a temperature in excess of 350 F., but substantially not in excess of 700 F. while such gases are maintained under pressures exceeding 40 atmospheres but not substantially exceeding 100 atmospheres, and then bringing the gases under said condition of temperature and pressure into contact with a catalyst consisting of a metal belonging to the 8th group of the periodic series, whereby to form additive hydrocarbon compounds of higher molecular weights by polymerization without substantial cracking and under exothermic conditions.

2. The process of manufacturing gasolinelike hydrocarbons from unsaturated hydrocarbon gases of the ethylene series which consists in the steps of heating such gases to temperatures in excess of 350 F. but substantially not in excess of 700 F. While said gases are maintained under pressures exceeding 4.0 atmospheres but not substantially exceeding 100 atmospheres, and then bringing thegases under said conditions into con-' tact with a catalyst belonging to the .8th group of the periodic series to form additive hydrocarbon compounds of higher molecular weights by polymerization without'substantial cracking.

3. The process of manufacturing gasolinelike hydrocarbons from unsaturated hydrocarbon gases of the ethylene series, which consists in the steps of heating such gases to temperatures in excess of 350 F. but substantially not in excess of 700 F. while such gases are maintained under pressures exceeding l0 atmospheres but no substantially exceeding 100 atmospheres, and then bringing the gases under said conditions into reaction promoting contact with a catalyst consisting of an alloy of metals belonging to the 8th group of the periodic series whereby polymerization takes place under exothermic conditions without substantial cracking.

4. The process of manufacturing gasolinelike hydrocarbons from unsaturated hydrocarbon gases of the ethylene series, which consists in the steps of heating such gases to temperatures in excess of 350 F. but substantially not in excess of 700 F. while such gases are maintained under pressures exceeding 40 atmospheres, but not substantially exceeding 100 atn'iospheres, and then bringing the gases under said conditions into contact with a catalyst comprising essentially palladium sponge whereby polymerization of hydrocarbon gases takes place under exothermic conditions and without substantial cracking.

5. The process of manufacturing gasolinelike hydrocarbons from unsaturated hydrocarbon gases of the ethylene series, which consists in the steps of heating such gases to temperatures in excess of 350 F. but substantially not in excess of 700 F. While such gases are maintained under pressures exceeding 40 atmospheres but not substantially exceeding 100 atmospheres, and then comprising a metal of the 8th group of the periodic series, the conditions being such that an exothermic reaction of polymerization takes place without substantial cracking.

In testimony whereof I aflix my signature.

CARY R. WAGNER.

bringing the gases under said conditions i 

